Process for breaking petroleum emulsions



Patented July 18, 1944 l UNITED STATES PATENT OFFICE PROCESS FOR BREAKING PETROLE EMULSIONS Melvin De Groote, University City, and Bernhard Keiscr, Webster Groves, Mo., assi ors to Petrolite Corporation, Ltd, Wilmington, Del., a corporation of Delaware No Drawing. Application June 15, 1942, Serial No. 447,168

Claims. (Cl. 252-341) This invention relates primarily to the resolu- Glycerol may be conveniently indicated by the tion of petroleum emulsions. v following formula:

The main object of our invention is to p de OH a novel process for resolving petroleum emulsions C H of the water-in-oiltype, that are commonly re- 5 ferred to as "cut oil, "roily oil, "emulsified oil," 0H etc., and which comprise fine droplets of'natural- If treated with an a kyl ting agent, and mo- 1y occur ring Waters or brmes dispersed in more mentarily consideration will be limited to an oxyor less permanent state throughout the oil which an ylating agent, one may obtain an oxyethylated constitutes the continuous phase of the emulsion. glycerql of the following formula typezv Another object is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions CzHgOr-(CzHiOhuH from mineral oil, such as crude petroleum and (C H O) ,H relatively softwaters or weak brines. Controlled l6 mulsification and subsequent clemulsification in which th value of u may vary from 3 to 10' under the conditions just mentioned i of sigand all the values of 11' need not be identical. nificant value in removing impurities, particu- If a polybasic carboxy acid be indicated by the larly inorganic salts, from pipeline oil. formula:

We have discovered that if one oxyalkylates c glycerol so as to introduce at least three oxyalkylene radicals for each hydroxy1 group, and it the product so obtained is reacted with a poly- 000E basic carboxy acid having not over eight carbon the n the acyclic reaction product of one mole of atoms, and in such a manner as to yield a fracoxyethylated glycerol and one mole of a polybasic tional ester, due to the presence of at least one free carboxyl radical, one can then esterify said cal-boxy acld may be indicated by the following acidic material or intermediate product with at formula" least one mole of an alcoholic compound of the type herein described to .give a variety of new CaHi a(C:H|O)-' compositions of matter which have utility in the (Cmohn demulsification of crude oil. The compounds herein contemplated may be in wh ch n has the value of one or two. Simiproduced in any suitable manner, but are usually larly, if two moles of the polybasic acid be used,

' manufactured by following one of two general then the compound may be indicated y e olprocedures. Inone of said procedures the oxylowing mrmula:

alkylated glycerfil, which is, in essence, a poly- (c,nio)..-ooca(coon)..-

hydric alcohol, is reacted with a polybasic acid camohwzmo) ,oocmcoom so as to give an acidic material or intermediate product, which, in turn, is reacted with an alco- (0,114)):

holic body of the kind hereinafter described, and 40 Likewise, if three moles of a polybasic acid are momentarily indicated by the formula R1(OH)m. employed, the compound may be indicated by the Generically, the alcoholic body herein conteme following f rmula:

plated may be considered a member of the class in which m may vary from 1 to 10, although the specific significance of m in the present instance CBHQOB (CIHlO)n'OOCR(COOHL," will be hereinafter indicated. The second pro- 0 H o #0001! COOH cedure is to react an alcohol of the formula type 1 4 I R1(OH)m with a polybaslc acid so as to produce If a-flactlonal ester of e kind ex plified by an intermediate product, and then react said the ee prec ing formulas is reacted with one intermediate product or fractional ester with the or more moles of an alcohol of the kind previousselected oxyalkylated glycerol. 1? des be in a generic Sense as R1(OH)m. then obviously, ma obtain a material or thetype indicated-by'-.theiollowing'formulaz (cm.o).'-oocn(ooon) .--1.

- cmmfiucimoisal-f (coon)? [(0.mo).-ooca 1 (000121).1

in himsical 0r 2, ills 0, 1 or 2, and dis 1,2 or3,anda:'is0or1,andy'is1or2.

It has been previously stated that compounds of the type herein contemplated may be obtained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide,-propylene oxide, butylene' oxide and glycid, which, although not included, strictly speaking, by the unitary structure CQHz O, is included. within the meaning of the hereto appended'claims and may be simply considered as a noamide.

variant'oi propylene-oxide, i. e., hydroxypropyl-' ene oxide. Similarly, where a carboxylic hydrogen atom'appears, it may be replaced by metal,

an ammoniumradical, or substituted ammonium radical, or by an organic group, derived from an alcohol, such as an aliphatic alcohol, an aralkyl converted into an amide, including a polyami- Thus, the preceding formula may be rewritten in its broader scope, as follows:

tion steps. As is well known, esteriilcation procedures can be carried out in various. manners,

but generally speaking, esteriflcations can be carrled out at the lowest feasible temperatures by using one or several procedures. One procedure is to pass an inert dried gas through the mass to be esterifled, and have present at the same time a small amount of a catalyst, such as dried HCl gas, a dried sulfonic acid, or the like. Another and better procedure, in manyinstances,-is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap out the water and return the liquid to the reacting vessel. This procedure is commonly employed in the arts; and for convenience, reference is made to U. 8. Patout No, 2,264,759, dated December 2,- 1941, to Paul C. Jones;

Referring again to the last two formulas indicating the compounds under consideration, it

can be readilyv understood thatsuch compounds,

in numerous instances, have the property of polyfunctionality. In view of this fact, where there is at least one residual carboxyl and at least one residual hydroxyl, one would expect that under suitable conditions," instead ofobtaining the monaseavu omeric. compounds indicated, one would, in reality, obtain a polymer in the sense, for example, that polyethylene glycols represent apolymer of ethylene glycol. The term .polymer is frequently used to indicate the polymerized product derived from a monomer in which the polymer has the same identicalcomposition as the mononier. In the present instance, however, polymerization involves the splitting and loss of water so that the process is essentially self-esterification. Thus, strictly speaking, the polymeric compounds are not absolutely isomers of the monomeric compounds, but since, for all practical purposes, they can be so indicated, and since such practice is common in the arts concerned with materials of this type, it is so adopted here. Thus,

ucts of the monomeric compounds.

' alcohol, or an alicyclic alcohol. It may also be In view of what has been said, and in .view of the recognized hydrophile properties of the recun'ing oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearlywater-soluble through self-emulsifying oils, to materials which are the balsam-like and sub-resinous or semi resinous in nature. The compounds may, vary from monomersto polymers, in which the unitary struca or 12 times.

ture appears a number of times, for instance,- 10 His to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent,for instance, at least 5% in some solvents, such as water,'alcohol, benzene, di-' chloroethyl ether, acetone, cresylicacid, acetic acid, ethyl acetate, dioxane, or the like. This is v disclosed, which contain neither a free hydroxyl nor a free ,carboxyl group, and one may also obtain a compound of the type in which there is present at least one. free carboxyl, or-at least one.

free hydroxyl, or both. The 'word "polar has' 1 a sometimes been used in the arts in this particular sense to indicate the presence of atv least one free hydroxyl group, or at least, one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen atom may, of

course, be replaced by any ionizablehydrogen.

atom equivalent, such, for example, as a metal, an ammonium radical, a substituted ammonium radical, etc. In the hereto appended claims the word polar is used in this specific sense,

We are aware that compounds-similar to those contemplated in the present instance may be derived from poly'hydroxylated compounds having more than three hydroxyl groups. For instance, they may be derived from acyclic diglycerol, triglycerol, tetraglycerol; mixed polyglycerols, mannitol, sorbitol, various hexitols, dulcitol, pentaerythritol sorbitan, mannitan, dipentaerythritol monoether,- and other similar compounds. Such particular types in which higher hydroxylated materials are subjected to oxy-' alkylation and then employed in the, same manner as xyalkylated glycerol ls employed in the v 1 I a present instance, are not contemplated in this specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be used as reactants to.

gen atom, particularly, when present in alow molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyDacetamide, the acetamide of tris(hydroxymethyDaminomethane, tetrahydroxylated ethylene diamine, etc. Compounds may also be derived from cyclic diglyceroi and the like. A

Furthermore, for convenience, attention is directed to a somewhat similar class of materials which are described in our co-pending application Serial No. 410,087, filed September 8, 1941 now Patent No. 2,329,699, dated Sept. 21, 1943. Said .co-pending application involves the use of the same type of alcoholic bodies for reactants, but is limited, among other things, to the compounds which are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than eight carbon. atoms, for example, oxalic, malcnic, succinic, glutaric, adipic, maleic, and phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester,

and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials. and greater care must be employed if the ultimate or final product be of a sub-resinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon atoms or less. Generally speak sing, the higher the temperature employed, the

easier it is to obtain large yields of esterified product, although polymerization may be stimulated. Oxalic acid may be comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. is available in the form of an anhydride, such anhydride is apt to produce the ester with greater Similarly, when a polybasic acid ease than the acid itself. For this reason, maleic anhydride is particularly adaptable, and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid or the anhydride has many attractive qualities of maleic anhydride, and this is alsotrue of adipic acid. For purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, reference is made to derivatives obtained by oxyethylation, although, as previously pointed out, other oxyalkylating agents may be employed.

. As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our pref- OxYErHYLa'rEn GLYCEROL Example 1 194 pounds of glycerol is mixed with /2%. by weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts, for instance, about 44 pounds at a time. The temperature employed is from C. Generally speaking, the gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is complete,

drops to zero, due to complete absorption of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for instance, 44 more pounds of ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained. This represents 660 pounds of ethylene oxide for 192 pounds of glycerol.

OXYETHYLATED GLYCEROL Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mole of glycerol. Otherwise, the same procedure is followed as in Example 1, preceding.

OXYETHYLATED GLYCEROL Example 3 The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 21 to one.

OXYETHYLATED GLYCEROL MALEATE Example 1 One pound mole of oxyethylated glycerol (1 to 15 ratio) prepared in the manner previously described is treated with one pound mole of maleic anhydride and heated at approximately 110 C. for approximately thirty minutes to two hours. with constant stirring, so as to yield a monomaleate.

OXYETHYLATED GLYcsRoL MALEATE Example 2 The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

'Oxxrrnrmrrn GLYcrRoL Mnmrr Example 'OxYErHYLArEn GLYCEROL MALEATE Example 4 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15) OXYETHYLATED GLYcnRor. MALEATE Example 5 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 21) is employed instead of oxyethylated glycerol (ratio 1 to 15) or (1 to 18).

' rived from higher fatty acids, such as stearic acid,

Previous reference has been made to an-alcoholic body which has been defined generically by the formula R1(OH)m. The sub-generic class of alcoholic compounds employed as'reactants is -interrupted at least once by an oxygen atom.-

in the manufacture of the present compounds,

Such ether linkages in the hydroxylated radical may occur asmany as five times. Such hydroxylated high molal amines are obtained by conventional procedure, in which a high molal primary or secondary amine is submitted to the action. of an oxyalkylatingagent, such as ethylene oxide, propylene oxide, butylene -oxide,

glycid, and .the like. The oxyalkylating agents employed are the kind which contain 4 carbon atoms or less in the hydrocarbon radical.

Our preferred oxyalkylating agent is ethylene oxide, due to its availability, comparatively low cost, and its increased reactivity in comparison with other 'oxyalkyla ting agents.

As to patents-which illustrate the oxyalkylation o! high molal amines, reference is made to 11.8.

Patent No. 2,233,383, dated February 25, 1941, to

De- Groote and Kaiser. See Examples 2, 8 and 14 in said De Groote and Keiser patent. Seealso U. S. Patent No. 1,970,578, dated August 21, 1934, to Schoeller and Wittwer. v

Amines of the kind enumerated which are used as primary reactants for themanufacture of hydroxylated high molal primary. or secondary amines, may be produced in various manners. They may be produced from naphthenic acids, resin acids, fatty acids, oxidized petroleum acids,

' or the like, by converting the acid into the ester,

preferably the ethyl ester or the like, and then converting the ester into the alcohol. Such alcohols, derived from various fatty acids, naphthenic acids, oxidized petroleum acids, resin acids, and the like, are available commercially and are employed in the manufacture of wetting agents or the like by sulfating or sulfonating such alcohols. Such high molal alcohols can be converted into the chlorides, and the chlorides reacted with am- J monia or a primary or secondary amine to give.

amines of the type herein contemplated. If dethe hydrocarbon chain is simply an alkyl radical. Naturally, it derived from an unsaturated fatty acid, such as oleic acid, the radical would represent an unsaturated hydrocarbon radical. If derived from ricinoleic acid or some other hydroxy acid,'such as hydmxy tearic acid, one would have a hydroxylated hydrocarbon radical.

In actual'practice amines ,of the kind herein contemplated can be obtained in various ways. Reference is made to a numberof patents which disclose or describe such amines, or the method of manufacturing the same. In some cases obvious' modifications will be required to produce amines of the kind contemplated; but such modiflcations would be evident to a skilled chemist, without further discussion. See the following patents:-

U. S. Patent No. 1,951,469, Bertsch, March 20, 1934; 2,006,058, Olin, June 25, 1935; 2,033,866, Schrauth, March 10,1936; 2,074,380, Flett, March 23, 1937; 2,075,825, Nafash, April 6, 1937; 2,078,922, Arnold, May 4, 1937; 2,091,105, Pigott, Aug. 24, 1937; 2,108,147, Spear, Feb. 15, 1938; 2,110,199, Carothers, March 8, 1938; 2,132,902,1-enher, Oct. 11, 1938; 2,178,522, Ralston, Oct. 31, 1938; British PatentNo. 359,001, to Johnson, on behalf of I. G. Farbenindustrie, A. G. 1932, and British Patent No, 358,114, to Carpmeal, on behalf of I. G. Farbenindustrie, A. G. 1932.

See also Industrial and Engineering Chemistry, industrial edition, volume 32, No. 4 (1940), p. 486.

It? view of what has been said, it will be noted that the group introduced into the amine and derived at least hypothetically from an acid is really' the carbon chain radical of the acyl group of the acid or hypothetical acid, along with what was at least hypothetically the carbonyl carbon atom. For the sake of convenience, this radical will be referred to as a hydrocarbon radical; and it is intended to include derivatives 'in' which a hydrogen atom or 'a' small number of hydrogen atoms have been replaced by the hydroxyl radical; for instance, the hydroxy hydrocarbonradical which would be supplied by-ricinoleicacid, hydroiwstearic acid, dihydroxystearic acid, or the like. In the present instance such usage seems eminently correct, in that the hydroc irbon radical supplies the hydrophobe portion of the amine, and this hydrophobe portion is not changed markedly by the presence of one or two hydroxyl groups, as are present in the case of ricinoleic acid, hydroxystearic acid, or the like; and such hydroxyl groups are essentially non-functional, in that they are not relied upon to supply points of chemical activity. They may slightly decrease the hydrophobe character of the radical to some. degree; but this cannot be significant, as can be appreciated by reference to ricinoleic acid. Since the carbon atom chain supplied to theamine by means of ricinoleic acid has 18 carbon atoms, it would appear relatively immaterial whether there was present one hydroxyl group or.

for example, the group or radical which would be obtained from ricinoleic acid.

v Certain facts are obvious in the preparation ofthe hydroxylated amines. If a secondary ,amine is employed as a primary reactant, then obviously, only one'hydroxylated radical can be ,amine; hexadecylamine; amine, etc.

amine, ethyl decylamine, propyl decylamine, etc.

Our preference is to use primary amines as raw materials, rather than secondary amines, and particularly amines which have been derived from carboxy acids. For instance, note the following: Octadecenylamine; cetylamine; stearylamine; oleoamine; ricinoleoamine; amines derived from naphthenic acids; amines derived from octadecadiene 9,11-acid-1; octadecylamine; amines derived from mixed unsaturated fatty acids, such as soyabean fatty acids; cottonseed oil fatty acids; linseed oil fatty acids; heptadecyldodecylamine; decyl- Attention is also directed to the fact that suitable amines can be derived from oxidized wax acids. As to the nature of these acids, see U. S. Patent No. 2,242,837, dated May 20, 1941, to Shields. It is well known that certain varieties of such wax acids contain approximately 22-26 carbon atoms, whereas, oxidized acids containing fewer carbon atoms are also available. It is again desirableto note thatthe high molal hydrocarbon group joined to the amino nitrogen atom may be aliphatic, alicyclic, aryl, or aralkyl in nature, as, for example, hydroxylatedamines obtained by the oxyalkylation of naphthylamine,

or the like,and substituted naphthylamines, such as alkylated naphthyiamines. Attention is directed to the fact that the amines in which there is no aryl group directly joined to the amino nitrogen atom, are comparatively basic in nature, 1. e., the type which has previously been indicated as aliphatic, alicyclic, or aralkyl. It is our preference to use the basic type; i. e., we have found hydroxylated high molal amines in which there isno aryl group directly joined to the amino nitrogen atom, to be the most desirable type of reactant for producing the new composition of matter, particularly when it is employed as a demulsifying agent.

In view of what has been said previously, and particularly, since the treatment of high molalamines with an oxyalkylating agent is a wellknown procedure, it does not appear necessary to elaborate further on this phase of the manufacturing procedure. However, the following examples are included by way of illustration:

HYDROXYLATED Hrcn Momr. AMINE Example 1 One pound mole of octadecenylamine is treated with two pound moles of ethylene oxide in the conventional manner to give the dihydroxylated compound.

HYDROXYLATED HIGH MOLAL Ami:

Example 2 Cetylamine is substituted for octadecenylamine in Example 1, preceding.

Hxnnoxrmrsn Hrcn Mouu. Am

, Example 3 Oleoamine is substituted for octadecenylamine 5 in Example 1, preceding.

HYDROXYLATED Hrcrr MOLAL AMINE Example 4 Ricinoleoamine is substituted for octadecenylamine in Example 1, preceding.

HYDROX YLATED HIGH MOLAL AMINE Example 5 Amine derived from naphthenic acids are substituted for octadecenylamine in Example 1, preceding.

HYUROXYLATED HIGH MOLAL Arum:

Example 6' Octadecylainine is substituted for octadecenylamine in Example 1, preceding.

Hvnnomaran Hrcn Morin. AMINE Example 7 Amines derived from mixed unsaturated fatty acids, such as soyabean fatty acids, cottonseed oil fatty acids, teaseed oil fatty acids, etc., are employed instead of octadecenylamine, in Example l, preceding.

HYnsoxYLAran HIGH Moan. Arum:

Example 8 Amines derived from abietic acid are employed instead of octadecenylamine, in Example 1, preceding.

Hxnaoxxnaran HIGH MOLAL AMINE Example 9 Amines derived from oxidized wax acids are employed instead of octadecenylamine in Example l, preceding.

Hvnnoxvmran HIGn Mom. Alana:

Example 10 The same procedure is followed as in Examples 1-9, preceding, except that 4 moles of ethylene oxide are employed instead of 2 moles.

HYDROXYLATED Hrcn MOI-AL AMINE Example 11 The same procedure is followed as in Examples 1-9, preceding, except that 6 moles of ethylene oxide are employed instead of 2 moles.

Hxnnoxmran Hrcn MOLAL Am: Example 12 The same procedure is followed as in Examples 1-9, preceding, except that 10 moles of ethylene oxide are employed instead of 2 moles.

Commarnn Moxouaarc DERIVATIVE Example 1 One pound mole of a product of the kind described under the heading Oxyethylated glycerol maieate, Example 1" is reacted with one pound mole of bis(hydroxyethyl) octadecylamine, preferably in the absence of any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a higher boiling range than xylene, and sometimes removal of porizing solvent, if employed, might be permitted to remain in the reacted mass and appear as a constituent or ingredient of the final product. In any event, our preferencev is to conduct the v reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of water. The temperature ofreaction is about 180 to 200 C. and time of reaction about 20 hours. I

Courrsrsn Mouoimuc Dsiuvarrvs Example 2 The same procedure is followed as in Completed monomeric derivative, Example 1, preceding, ex-

. cept that the dimaleate described under the heading Oxyethylated glycerol maleate, Example '2 is used instead of the monomaleate.

Courtnrsn Monormiuc DsaIvA'rIvr:

Example 3 I The same rocedure is followed as in the two preceding'examples, except that the trimaleate is substitutedfor theinonomaleate or dimaleate 'in the two preceding examples.

Commirrn MoNonraIcDsaIvArrvr Example 4 The same procedure is followed 'as in Examples 2 and 3, immediately preceding, except that for each pound mole of the maleate, or each pound mole of the trimaleate, instead of using'one pound mole of bis(hydroxyethyl)octadecylamine, one employs two pound moles.

Comrntrsn Monouz uc Ezample 5 Dmuvxrrva The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate, instead of adding one pound mole of Comrrsrso Morroimiuc lbssrvarrvs temple '7 The same procedure is followed as in Example- 6, immediately preceding, except that the oxyethylated glycerol employed represents one hav ing an even higher degree of oxyethylation. Forexample, one indicated by the ratio of l to 21. (See Oxyethylated glycerol maleate, Example 5, preceding.)

ComrLsrsn Monomeric Danrwrrrvr: v l I Example 8 The same procedure is followedas in Exampies 1-7, preceding, except the amine employed is of the kind described under the heading Hydroxylated high molal amine, Example 10."

, 100% yields are the exception, rather than the ;such solvent might present a difllculty. In other, 'instances, however, such high boiling inert va-' commr'rnn Monomuuc Daniwgrrvs Example 9 The same procedure is followed as in Examples 1-7; preceding. except that the amine employed is of the kind described'under the heading "Hydroxylated high molal amine, Example 11."

COMPLETED Monommuc Daxrvarrvx) Example 10 a nitrogen or dried carbon dioxide, may be passed through the mixture. Sometimes it is desirable to add an esteriflcation catalyst, such as sulfuric acid, benzene sulfonic acid, or the like. This is the same general procedure as employed in the.

manufacture of ethylene glycol dihydrogen di- 'phthalate. (See U. S. Ratent No. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esteriflcation is conducted most readily in the presence of an inert solvent, that carries away the water ofesteriflcation which maybe formed, although as is readily'appre ciated, such water of esteriflcation is absent when such tym: of reaction involves an acid anhy dride, such as maleic anhydride, and a glycol. However, if water is formed, for instance, when citricacid is employed, then a solvent such as xylene may be present and employed to carry oil the water formed. The mixture of xylene vapors and water, vapors can be condensed so that the water is separated. The xylene is then returned to the reaction vessel for further circulation. This is a conventional and well-known procedure and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, in spite of precautions, at least This is typical, of course, of organic reactions of this kind, and asis well known, organic reactions per se are characterized by the fact that rule, and'that significant yields are satisfactory, especially inthose instances where the by-prodnets of cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance; In many cases when the com-pound is manufactured for purposes of demulsification, one is better off-to obtain a polymer; in the sense previously described, particularh a polymer whose molecular weight isa rather small multiple of the molecular weight of the monomer, for instance. a polymer whose molecular weight 'is .two, three, four, live. or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus, in instances where it is necessary to have. a maximumyield of the monomer, it may be necessary to take such precautions that the algali used in promoting oxyethylation of glycerol, be removed before subsequent reaction. This, of course, can-be done in any, simple manner by conversion to sodium chlioride, sodium sulfate, or any suitable proceure. I

In the preceding examples of the Completed monomeric derivative. Examples 1 to 10. inclusive, no reference is made to the elimination of such alkaline catalyst, in view of the effectiveness of the low multiple polymers as demulsiflers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents, including organic radicals, for .instance, the radicals obtained from alcohols, hydroxylated amines, non-hydroxylated amines, polyhydric alcohols, etc. Obviously, the reverse is also true, in that a free hydroxyl group may be esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxyacetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above fact in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that by-products or cogeneric materials were formed, may be recapitulated with greater definiteness,- and one can readily appreciate that the formation of heatrearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the products herein contemplated may be characterized by being monomer of the type previously described, or esterification polymers, or the heatrearranged derivatives of the same, and thus including the heat-rearranged derivatives of both the polymers and esterification monomers, sep-' arately and jointly. Although the class of materials .specifically contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, ex-

cept in a manner employed in the hereto appende :1 claims.

Although the products herein contemplated vary so broadly in their characteristics, i. e., monomers through sub-resinous polymers, soluble products, water-emulsifiable oils or compounds,

hydrotropic materials, balsams, sub-resinous materials, semi-resinous materials, and the like, yet

there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation, particularly the oxyethylation of the glycerol used as the raw material. As hereinafter indicated, in the resolution of oil field emulsions, the demulsifier may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000,

1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one can not differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble material are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position prevlously occupied perhaps by the emulsifying colloid. In any event, reviewed in this light, the obvious common property running through the entire eries, notwithstanding variation in molecular size and physical make-up, is absolutely apparent. Such statement. is an obvious oversimpliflcation of the rationale underlying demulsification, and does not even consider the resistance of an interracial film to crumbling,

' displacement, being forced into solution, altered wetability, and the like. As to amidification poly-.

mers, for instance, where Z is a polyaminoamide radical, see what i said subsequently.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 1 A polyfunctional monomeric compound of the kind described under the headings "Completed monomeric derivative, Examples 1 to 7, preceding, i heated at a temperature of 220-240 C., with constant stirring, for a period of 2 to- 60 hours, so as to eliminate sufl'lcient water in order to insure that the resultant product has a molecular weight approximately twice that of the initial monomer.

COMPLETED POLYMERIC DERIVATIVES INCLUDING I-IEAT-REARRANGED COGENERS Example 2 COMPLETED POLYMERIC DERIvA'rIvEs INCLUDING I-IEA'r-REARRANGED COGENERS Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one Dolymerizes a mixture instead of a single monomer, for instance, a mixture of materials of the kind described in Completed monomeric derivative, Example 3, andin Completed monomeric derivative, Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymerized product need not be obtained as a result of a two-step procedure. In other'words, one need not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer in one step. Indeed, the formation of the monomer and polymerization may take place simultaneously. This is especially true if polymerizationis conducted in the absence of a liquidsuchas xylene. as previously described, and if one uses a comparatively higher temperature, for instance, approximately 220 C. for polymerization- Thus, one pound mole of an oxyethylated glycerol polymaleate of the kind previously described is mixed with a mole of bis(hydroxyethyl) octadecylamine and reacted for approximately 30 hours, at approximately 220 0.,

until the mas is homogeneous. It is stirred con- The fact that the polymerized and heat-rearranged products can be made in a single step, illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants lesser degree, sufllcient monomeric materials so. v that a homogeneous system is present. Subse quently. as reaction continues, ,the system may become heterogeneous and exist in two distinct" phases, one being possibly an oily body of -moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances it will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by separating the. two heterogeneous phases and employing each as if it were a separate product of reaction. I J

Conventional demulsifying agents employed, in the treatment ofoil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons such as gasoline, kerosene, stove oil, a coal tar product such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethylalcohol, denatured alcohol,v propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such'as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. herein described, when employed as demulsifiers Similarly, the material or materials for 'water-in-oil emulsions, may be admixed with one or more of the solvents customarily used inconnection with conventional, demulsifying agents, provided that such compoundsare compatible. They will be compatible with the hydrophile type ofsolvent in all instances. Moreover, said material or materials may be usedalone, or in admixture with other suitable wellknown classes of demulsifying agents.

It is well-known that conventional demulsifV- ing agents may be used in a water-soluble form.

or in an oil-soluble form, or in a form exhibit ing both oil and water-solubility. Sometimes they may be used in a form which exhibits I818! tively limited oil-solubility. However, since such reagents are sometimes used in a ratio oil to 10,000, or 1 to 20,000, or even 1 to 30,000, suching petroleum emulsions of the water-in-oil type, t a treating agent or demulsifying agent of the d above described is broughtinto contact with or caused toact upon the emulsion to be treated,

in any "of the various ways, or by any of the variousapparatus now generally used-to resolve or breaki petroleum emulsions withlarchemical reagent, the above procedure being used, either alone, or in combination with other demulsifying procedure, such as the electrical dehydration process. I

The demulsifierherein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifier in contact with the fluids of the well atthe bottom .of the well, or'at some point prior to their emergence. This particularv type of application is decidedly feasible when the de-' mulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification. I

I cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction vessel speeds upreaction-and polymerization, compared with a glass-lined vessel.-

As has been previously indicated, the subgenus employed as .an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pen'ding applications Serial Nos. 447,151, 447,152, 447,153.

447,154, 447,155, 447,156, 447,157, 447,158, 447,159, 447,160, 447,161, 447,162, 447,163, 447,164, 447,165, 447,166, and 447,167, filed June 15, 1942.

Havin thus described our invention, what we I I fier comprising a member 101 the class consisting lowing formulaz.

an apparent insolubiiity-in'oil and water is not ployed. This same fact is true in regard to the the reagent ordemulsifying agent contemplated material or materials herein described, except that-they are invariably water-soluble.

We desire to point out that the superiority of in our herein described process forbreaking pef troleum emulsions, is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other availabledemulsiflers, or conventionalmixare concerned; but wehave found that such a demulsifying agent has commercial value, as it will economically break or resolve .oil fieldlemulw sions in a number of cases which cannot be treat-.

significant, because said reagents undoubtedly 7 1 have solubility within the concentration em of monomers, sub-resinous esterification polymats, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the folin which is the carboxyl-free radical ot La polybasic carboxy acid having not over -8' carbon hydroxylated aliphatic radical: to the extent that such radical'contains etherlinkages, ,such ether linkages shall not exceed 5 and'the alkylene rad ical of said aliphatic radical containing not over 4 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n-represents the numerals 2 to 4: 1t? represents .thenumerals 3 to 10; n" represents the. numerals 1 to 2; :1: represents thenumerals10 to 2;

yrepresents the numerals 0 to:2: 2 represents the numerals 1 to 3; 1: represents the numerals to 1; and 11' represents the numerals 1 to 2.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub- Jecting the emulsion to the action of a demulsi: fler comprising a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

c.Ht.0).'o0cR000z1.

clmoa-uoimnon nl,

[(cimnmooocncooall.

in which R is a carboxyl-free radical'of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a hydroxylated high molal amine radical, having at least 1 hydrocarbon radical containing at least 8 carbon atoms and not more than 26 carbon atoms, and having at least 1 hydroxylated aliphatic radical; to the extent that such radical contains ether linkages, such ether linkages shall not exceed and the alkylene radical of said aliphatic radical containing not over 4 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 2 to 4; n represents the numerals 3 to .1: represents the numerals 0 to 2; 1! represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub- Jecting the emulsion to the action of a demulsifier comprising a member of the class consisting of monomers, sub-resinous esteriflcatlon polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula: v lwimowoocncoozl.

cantoramona '(vimowoocncooail.

in which R-is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms;

' R1 is a hydroxylated high molal amine radical,

having-at least 1 hydrocarbon radical containing at least 8 carbon atoms and not more than 26 carbonfatoms, and having at least 1' hydroxylated aliphatic radical; to the extent that such radical contains ether linkages, such ether linkages shall not exceed 5 and the alkylene radical of said aliphatic radical containing not over 4 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11' represents the numerals 3 to 10; a: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a polar member .of the class con- 5 sisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

in which R is a carboxyl-free radical of a dlbasic carboxy acid having not over 6 carbon atoms; R1 is a hydroxylated high molal amine radical, having at least 1 hydrocarbon radical containing at least 8 carbon atoms and not mor than 26 carbon atoms, and having at least 1 hydroxylated aliphatic radical; to the extent that such radical contains ether linkages, such ether linkages shall not exceed 5 and the alkylene radical of said aliphatic radical containing not over 4 carbon atoms; Z is an acidic hydrogen atom equivalent including "the acidic hydrogen atom itself; n represents the numerals 3 to 10; a: represents the numerals 0 to 2; 1! represents the nutgngrals Oto 2; and .2 represents the numerals 1 -5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler comprising a polar acidic member of the class consisting of monomers, sub-resinous esteriflcation polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

[(o|11.o)..'0ocacooz z CIHBOH(CIH4O)I'H]| (C2H40)- 'OOCRCO om]. in'which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; 45 R1 is a hydroxylated high molal amine radical,

having at least 1 hydrocarbon radical containing at least 8 carbon atoms and not more than 26 carbon atoms, and having at least 1 hydroxylated aliphatic radical; to the extent that such radical contains ether linkages, such ether linkages shall not exceed 5 and the alkylene radical of said aliphatic radical containing not over 4 carbon atoms: Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n

represents the numerals 3 to 10; :arepresents the numerals 0 to 2; 11.! represents the numerals 0 to 2; and z represents the numerals 1 to 3.

MELVIN DE GROOTE. BERNHARD KEISER. 

